EP2917179B1 - Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure - Google Patents
Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure Download PDFInfo
- Publication number
- EP2917179B1 EP2917179B1 EP13776762.0A EP13776762A EP2917179B1 EP 2917179 B1 EP2917179 B1 EP 2917179B1 EP 13776762 A EP13776762 A EP 13776762A EP 2917179 B1 EP2917179 B1 EP 2917179B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- weight
- hydrogen peroxide
- equilibrium peracetic
- equilibrium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims description 217
- 238000000034 method Methods 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 114
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 95
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011541 reaction mixture Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- 238000003860 storage Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000645 desinfectant Substances 0.000 description 6
- 230000000249 desinfective effect Effects 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000137 polyphosphoric acid Polymers 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011067 equilibration Methods 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- HJPIFBJPTYTSEX-UHFFFAOYSA-N 2h-tetracen-1-one Chemical compound C1=CC=C2C=C(C=C3C(=O)CC=CC3=C3)C3=CC2=C1 HJPIFBJPTYTSEX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LNQCJIZJBYZCME-UHFFFAOYSA-N iron(2+);1,10-phenanthroline Chemical compound [Fe+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 LNQCJIZJBYZCME-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
- C07C409/26—Peracetic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
Definitions
- the invention relates to a process for the preparation of equilibrium peracetic acid and obtainable by the process equilibrium peracetic acid low corrosivity.
- Peroxyacetic acid is used as a disinfectant, which already at low temperatures has a broad effect against bacteria and other microorganisms, as well as against viruses and against which bacteria and viruses do not resist.
- Peroxyacetic acid has the advantage that at the application concentrations that are used for disinfection, after a time complete hydrolysis to acetic acid and hydrogen peroxide takes place, so that the biocidal effect is lost and it can not lead to an accumulation of biocide.
- Peroxyacetic acid is usually marketed in the form of equilibrium peracetic acid, which is brought to the desired concentration of use for application with water.
- equilibrium peracetic acid is a mixture which contains peroxyacetic acid, hydrogen peroxide, acetic acid and water in chemical equilibrium.
- the chemical equilibrium is established between these four components according to the following reaction equation: CH 3 C (O) OH + H 2 O 2 ⁇ CH 3 C (O) OOH + H 2 O
- Equilibrium peracetic acid is usually prepared from acetic acid and aqueous hydrogen peroxide solution by adjusting this equilibrium. The adjustment of the balance takes place in the absence of other components, however, only slowly and requires at 20 ° C for several days. To accelerate the adjustment of the equilibrium therefore usually sulfuric acid is added as a catalyst. Addition of larger amounts of sulfuric acid also allows in disinfection applications to control the metered amount of peroxyacetic acid through the conductivity of the disinfecting solution.
- Equilibrium peracetic acid containing sulfuric acid has the disadvantage that it has a corrosive effect on metallic materials and that it can not be stored in contact with stainless steel, since iron ions dissolved out of the material catalyze the decomposition of peroxyacetic acid.
- JP 10-330357 describes a preparation of peroxyacetic acid by reacting butyl acetate with 60 wt .-% hydrogen peroxide solution with the addition of methanesulfonic acid as a catalyst. The reaction in the absence of a carboxylic acid corrosion problems should be avoided.
- the utility model DE 20 2007 005 732 U1 describes a cleaning agent for removing solid deposits in drinking water pipes containing 1 to 14% by weight of sulfamic acid, 5 to 10% by weight of methanesulfonic acid, 0.075 to 0.15% by weight of phosphonobutane tricarboxylic acid, 0.3% by weight of 2-propanol and contains 100% supplementary water.
- the detergent can be provided by adding 1 to 10 wt .-% disinfectant with a disinfecting effect, which can be used as disinfectant hydrogen peroxide-containing substances such as peracetic acid.
- compositions for the dissolution of oxalate deposits containing methanesulfonic acid and additionally phosphoric acid or nitric acid may contain one or more additives, among others, as disinfectants, bromoacetic acid, peracetic acid, salicylic acid and hydrogen peroxide.
- the invention therefore provides a process for the preparation of equilibrium peracetic acid by reacting acetic acid with hydrogen peroxide in an aqueous reaction mixture, the reaction being carried out in the presence of methanesulfonic acid as the catalyst.
- the invention also provides the use of methanesulfonic acid as catalyst for the preparation of equilibrium peracetic acid from acetic acid and hydrogen peroxide.
- Another object of the invention is an equilibrium peracetic acid comprising peroxyacetic acid, hydrogen peroxide, acetic acid and water and containing methanesulfonic acid.
- acetic acid and hydrogen peroxide are reacted in aqueous reaction mixture in the presence of methanesulfonic acid to give equilibrium peracetic acid.
- Methanesulfonic acid acts as a catalyst, which increases the rate of reaction of acetic acid with hydrogen peroxide to peroxyacetic acid.
- the reaction is preferably carried out until the content of peroxyacetic acid has reached more than 90% and more preferably more than 95% of the content present in the chemical equilibrium.
- the reaction mixture for the reaction of acetic acid with hydrogen peroxide contains 0.1 to 2.0% by weight of methanesulfonic acid, more preferably 0.5 to 2.0% by weight of methanesulfonic acid.
- the reaction mixture for the reaction of acetic acid with hydrogen peroxide contains from 5 to 30% by weight of methanesulfonic acid.
- methanesulfonic acid in this concentration range, an equilibrium peracetic acid can be obtained whose dosage for disinfection applications can be controlled by the electrical conductivity of the dilute solution and which has a substantially lower corrosive action than an equilibrium peracetic acid containing suitable amounts of sulfuric acid for the same purpose Has metals.
- the heat development in the reaction mixture is significantly lower than when using an appropriate amount of sulfuric acid.
- acetic acid can be used in pure form or in the form of an aqueous solution.
- acetic acid is used in pure form.
- Hydrogen peroxide is preferably used in the form of an aqueous solution with a content of 10 to 85 wt .-%, particularly preferably 25 to 60 wt .-%.
- water may optionally be added to the reaction mixture.
- the aqueous reaction mixture contains no additional solvent besides water.
- the amounts of acetic acid, hydrogen peroxide and water in the reaction mixture are chosen so that after equilibration the desired content of peroxyacetic acid and hydrogen peroxide in the equilibrium peracetic acid is achieved.
- Acetic acid and hydrogen peroxide are preferably used in a molar ratio in the range of 0.5 to 10, particularly preferably 0.5 to 5.
- Methanesulfonic acid is used for the process according to the invention preferably in pure form or in the form of an aqueous solution, more preferably in the form of an aqueous solution containing from 1 to 40% by weight of water.
- the reaction mixture is prepared by mixing acetic acid, aqueous hydrogen peroxide solution containing from 25 to 60% by weight of hydrogen peroxide and methanesulfonic acid, wherein the methanesulfonic acid may contain from 1 to 40% by weight of water.
- acetic acid, hydrogen peroxide and methanesulfonic acid are added to the reaction mixture.
- Methanesulfonic acid is preferably added after mixing acetic acid and hydrogen peroxide or added to one of the starting materials acetic acid or aqueous hydrogen peroxide solution.
- the methanesulfonic acid is added to the hydrogen peroxide solution.
- acetic acid and aqueous hydrogen peroxide solution can be mixed batchwise with one another in the process according to the invention.
- acetic acid and aqueous hydrogen peroxide solution may also be mixed continuously, for example via a static mixer.
- a continuous mixing the in WO 02/26459 described methods are used.
- conversion to equilibrium peracetic acid can be made in any container. Since the heat of reaction of the Reaction is low, the reaction can be carried out without cooling and even adiabatic. In a preferred embodiment, the reaction takes place after mixing in a storage container or transport container for equilibrium peracetic acid.
- the equilibrium peracetic acid obtainable by the process of the present invention includes peroxyacetic acid, hydrogen peroxide, acetic acid, water and methanesulfonic acid.
- Peroxyacetic acid, hydrogen peroxide, acetic acid and water are in chemical equilibrium.
- the equilibrium peracetic acid according to the invention preferably contains from 2 to 24% by weight, more preferably from 3 to 17% by weight and in particular from 4 to 15% by weight, of peroxyacetic acid.
- the equilibrium peracetic acid of the present invention contains from 2 to 12% by weight of peroxyacetic acid and from 5 to 30% by weight of methanesulfonic acid and the weight ratio of methanesulfonic acid to peroxyacetic acid is in the range of 2 to 5.
- diluting the equilibrium peracetic acid may be based on Application concentration for disinfection applications can be controlled by the electrical conductivity of the diluted solution.
- the equilibrium peracetic acid according to the invention contains, in addition to peroxyacetic acid, hydrogen peroxide, acetic acid, water and methanesulfonic acid, up to 5% by weight of one or more surfactants.
- Suitable surfactants for use in equilibrium peracetic acid are known in the art, for example DE 26 16 049 A1 . EP 147 207 . WO 93/10088 .
- Preferred surfactants are anionic surfactants, such as alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates, and nonionic surfactants, such as fatty alcohol alkoxylates, fatty acid alkoxylates and tertiary amine oxides having a long-chain alkyl radical.
- anionic surfactants such as alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates
- nonionic surfactants such as fatty alcohol alkoxylates, fatty acid alkoxylates and tertiary amine oxides having a long-chain alkyl radical.
- the equilibrium peracetic acid according to the invention may additionally contain one or more stabilizers which stabilize peroxyacetic acid against catalytic decomposition by heavy metal ions.
- Suitable stabilizers for peroxyacetic acid are known in the art, for example EP 742 206 B1 , Paragraphs [0016] and [0017].
- Preferred stabilizers are 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), dipicolinic acid and their alkali metal salts.
- the equilibrium peracetic acid according to the invention may additionally contain one or more hardness-stabilizing compounds which can complex calcium and magnesium ions.
- Suitable hardness-stabilizing compounds for equilibrium peracetic acid are known from the prior art, for example from EP 945 405 B1 , Paragraph [0005].
- a polymer containing carboxyl groups is used as the hardness-stabilizing compound.
- polymers from the series (i) by oxidative polymerization of acrolein or acrolein and acrylic acid produced polymers, (ii) polyacrylic acid, (iii) copolymers of acrylic acid and another unsaturated carboxylic acid, especially maleic acid, and (iv) polymaleic acid, wherein the average molecular weight Mw of the polymer is in the range of 500 to 25,000, in particular 1,000 to 15,000. In of equilibrium peracetic acid, carboxyl groups of the hardness-stabilizing polymer may be partially converted into percarboxylic groups.
- the equilibrium peracetic acid according to the invention contains less than 1% by weight of additional compounds besides peroxyacetic acid, hydrogen peroxide, acetic acid, water, methanesulfonic acid, optionally up to 5% by weight of surfactants and optionally up to 10% by weight of polymers containing carboxyl groups.
- the equilibrium peracetic acid formed contained 15.2% by weight of peroxyacetic acid, 14.3% by weight.
- Hydrogen peroxide and 0.7 wt .-% methanesulfonic acid for this equilibrium peracetic acid, a self-accelerating decomposition temperature (SADT) of 50 ° C. for storage in a non-isolated test specimen UN H.2 for hazardous goods of UN class 5.2 was used in a 1 liter spherical autoclave with the addition of a pickled metal coupon 17.5 m 3 stainless steel tank determined.
- the UN Class 5.2 hazardous goods UN H.2 test method in a 1 l sample overadiabatic storage and two 20 * 60 * 2 mm HDPE plates in a 1 l spherical dewar became a self-accelerating decomposition temperature (SADT) of 70 ° C for storage in a 1 m 3 HDPE IBC.
- SADT self-accelerating decomposition temperature
- Example 8 1141.0 g of PERSYNTH® 500LC hydrogen peroxide 49.4% by weight, 567.6 g of acetic acid, 269.9 g of deionized water, 19.8 g of 98% by weight of sulfuric acid, 1.6 g of 1- Hydroxyethane-1,1-diphosphonic acid and 0.24 g of pyridine-2,6-dicarboxylic acid and reacted by standing at room temperature to equilibrium peracetic acid.
- the resulting equilibrium peracetic acid contained 14.5% by weight of peroxyacetic acid, 21.4% by weight of hydrogen peroxide and 1.0% by weight of sulfuric acid. 3 parts of the equilibrium peracetic acid were diluted with 997 parts of demineralized water to a disinfecting solution.
- the disinfecting solution thus obtained was stored at room temperature in contact with a material coupon (steel material number 1.0038 with the dimensions 60 * 20 * 3 mm), which was previously pickled for 1 h at 20 ° C with inhibited hydrochloric acid. After 24 h, the material coupon was clearly rusty and the solution discolored yellowish, the content of peroxyacetic acid had decreased to 2 ppm (determined with Merck Reflectoquant® test strips). From the weight decrease of the material coupon, a material removal of 0.4 mm / a was calculated. Without material coupon, the content of peroxyacetic acid after 24 h at 380 ppm and after 72 h at 370 ppm (colorimetrically determined with ABTS color reagent).
- Example 9 Example 8 was repeated, but instead of the sulfuric acid, 28.6 g of 70% by weight of methanesulfonic acid Lutropur MSA from BASF were used and the amount of deionized water was reduced to 261.2 g.
- the resulting equilibrium peracetic acid contained 14.6% by weight of peroxyacetic acid, 21.6% by weight of hydrogen peroxide and 1.0% by weight of methanesulfonic acid.
- the disinfectant solution prepared by dilution showed no discoloration on storage in contact with the material coupon and no change was visible on the material coupon after 72 hours. From the weight decrease of the material coupon a material removal of less than 0.01 mm / a was calculated.
- Example 10 1052.7 g of 49.4% by weight of PERSYNTH® 500LC hydrogen peroxide, 160.1 g of acetic acid, 479.7 g of deionized water, 306.2 g of 98% by weight of sulfuric acid, 1.4 g of 11- Hydroxyethane-1,1-diphosphonic acid and 0.18 g of pyridine-2,6-dicarboxylic acid and reacted by standing at room temperature to equilibrium peracetic acid.
- the resulting equilibrium peracetic acid contained 5.0% by weight of peroxyacetic acid, 23.7% by weight of hydrogen peroxide and 15.0% by weight of sulfuric acid. 1 part of the equilibrium peracetic acid was diluted with 99 parts of demineralized water to a disinfecting solution.
- the disinfecting solution thus obtained was stored in contact with a material coupon as in Example 8. After 15 minutes, the material coupon was clearly rusty, the solution was yellow discolored after 24 h and cloudy, the content of peroxyacetic acid had decreased to 7 ppm (determined with Merck Reflectoquant® test strips). From the weight decrease of the material coupon a material removal of 8 mm / a was calculated. Without Material coupon was the content of peroxyacetic acid after 24 h at 370 ppm (determined colorimetrically with ABTS color reagent).
- Example 10 Example 10 was repeated, but instead of the sulfuric acid, 428.7 g of 70% by weight of methanesulfonic acid Lutropur MSA from BASF were used and the amount of deionized water was reduced to 357.3 g.
- the resulting equilibrium peracetic acid contained 4.7% by weight of peroxyacetic acid, 23.9% by weight of hydrogen peroxide and 15.0% by weight of methanesulfonic acid.
- the disinfectant solution prepared by dilution showed no discoloration or haze after 48 h of storage in contact with the material coupon, and no change was visible on the material coupon after 48 h. From the weight decrease of the material coupon, a material removal of 2.7 mm / a was calculated.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Engineering & Computer Science (AREA)
- Detergent Compositions (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyrane Compounds (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13776762.0A EP2917179B1 (de) | 2012-11-08 | 2013-10-09 | Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure |
PL13776762T PL2917179T3 (pl) | 2012-11-08 | 2013-10-09 | Sposób wytwarzania kwasu nadoctowego w stanie równowagi i otrzymywany tym sposobem kwas nadoctowy w stanie równowagi |
SI201331132T SI2917179T1 (sl) | 2012-11-08 | 2013-10-09 | Postopek priprave ravnotežne perocetne kisline in ravnotežna perocetna kislina, pridobljena po tem postopku |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12191799 | 2012-11-08 | ||
EP13776762.0A EP2917179B1 (de) | 2012-11-08 | 2013-10-09 | Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure |
PCT/EP2013/071013 WO2014072143A1 (de) | 2012-11-08 | 2013-10-09 | Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2917179A1 EP2917179A1 (de) | 2015-09-16 |
EP2917179B1 true EP2917179B1 (de) | 2018-06-20 |
Family
ID=47189749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13776762.0A Active EP2917179B1 (de) | 2012-11-08 | 2013-10-09 | Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure |
Country Status (19)
Country | Link |
---|---|
US (1) | US9573893B2 (ja) |
EP (1) | EP2917179B1 (ja) |
JP (1) | JP6104397B2 (ja) |
KR (1) | KR102158059B1 (ja) |
CN (1) | CN104684892B (ja) |
AR (1) | AR093406A1 (ja) |
AU (1) | AU2013343772B2 (ja) |
BR (1) | BR112015007192B1 (ja) |
CA (1) | CA2890831C (ja) |
ES (1) | ES2684224T3 (ja) |
HK (1) | HK1210138A1 (ja) |
MA (1) | MA20150407A1 (ja) |
PL (1) | PL2917179T3 (ja) |
PT (1) | PT2917179T (ja) |
SI (1) | SI2917179T1 (ja) |
TW (1) | TWI603952B (ja) |
UY (1) | UY35124A (ja) |
WO (1) | WO2014072143A1 (ja) |
ZA (1) | ZA201503136B (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103704264B (zh) * | 2014-01-09 | 2016-04-20 | 南通思锐生物科技有限公司 | 一种消毒清洁剂 |
CN104304315A (zh) * | 2014-09-18 | 2015-01-28 | 魏巍 | 一种稳定的低腐蚀性杀孢子剂及其制备方法 |
US9907305B2 (en) | 2016-03-22 | 2018-03-06 | Solvay Sa | Production of disinfecting solutions |
AU2020282801B2 (en) * | 2019-05-31 | 2023-09-28 | Ecolab Usa Inc. | Method of monitoring peracid concentrations by conductivity measurements and peracid composition |
KR20230027624A (ko) * | 2021-08-19 | 2023-02-28 | 주식회사 휴온스메디텍 | 살균소독용 과아세트산 조성물 및 이의 제조방법 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3360531A (en) * | 1964-10-06 | 1967-12-26 | Ashland Oil Inc | In situ epoxidation process |
GB1203752A (en) * | 1966-09-30 | 1970-09-03 | Laporte Chemical | Preparation of lactones |
DE2616049A1 (de) | 1976-04-12 | 1977-10-27 | Henkel & Cie Gmbh | Lagerstabile konzentrate von funktionellen mitteln |
US4172086A (en) * | 1977-03-28 | 1979-10-23 | Fmc Corporation | Process for the manufacture of peroxycarboxylic acids |
US4115410A (en) * | 1977-09-15 | 1978-09-19 | Olin Corporation | Process for making peroxycarboxylic acid |
FR2521991A1 (fr) * | 1982-02-24 | 1983-08-26 | Air Liquide | Solutions commerciales de peracides carboxyliques stables et non corrosives et leurs applications |
GB8334249D0 (en) | 1983-12-22 | 1984-02-01 | Tenneco Organics Ltd | Disinfectants |
CN1034500C (zh) * | 1991-09-20 | 1997-04-09 | 艾尔夫·阿托彻姆公司 | 过丙酸的制备方法 |
GB9124160D0 (en) | 1991-11-14 | 1992-01-08 | Interox Chemicals Ltd | Stabilised peracid solutions |
DE19517465C1 (de) | 1995-05-12 | 1997-01-23 | Degussa | Percarbonsäurelösungen mit verbesserter Stabilität im Kontakt mit Edelstahl |
FR2759911B1 (fr) | 1997-02-26 | 1999-12-17 | Chemoxal Sa | Composition desinfectante a base d'acide peracetique et d'un agent tensioactif non-ionique |
EP0873687B2 (fr) | 1997-04-24 | 2006-04-26 | Chemoxal Sa | Composition désinfectante et fongicide à base d'acide péracétique et d'un oxyde d'amine |
JPH10330357A (ja) * | 1997-05-28 | 1998-12-15 | Arakawa Chem Ind Co Ltd | 過酸の製造方法 |
DE19812588C1 (de) * | 1998-03-23 | 1999-04-22 | Degussa | Härtestabilisierende Percarbonsäurelösungen, Verfahren zu deren Herstellung und deren Verwendung |
EP1004576A1 (en) * | 1998-11-23 | 2000-05-31 | SOLVAY (Société Anonyme) | Process for producing peracetic acid |
IT1315243B1 (it) * | 1999-10-15 | 2003-02-03 | Zambon Spa | Processo di ossidazione per la preparazione di intermedi utili nellasintesi di diarilpiridine |
DE10048513A1 (de) | 2000-09-29 | 2002-04-11 | Degussa | Verfahren zur kontinuierlichen Herstellung von Stoff- und Reaktionsgemischen und Vorrichtung zu seiner Durchführung |
FI112363B (fi) * | 2001-04-04 | 2003-11-28 | Kemira Chemicals Oy | Menetelmä peretikkahapon valmistamiseksi |
ITMI20012692A1 (it) * | 2001-12-19 | 2003-06-19 | Zambon Spa | Processo di ossidazione per la preparazione di intermedi utili nella sintesi di diarilpiridine |
CN1803771A (zh) * | 2006-01-23 | 2006-07-19 | 周新基 | 过氧乙酸的生产方法 |
DE202007005732U1 (de) | 2007-04-20 | 2007-07-12 | Edac Power Electronics Co., Ltd., Jhonghe | Ein Aufbau eines universellen Serial-Bus |
FR2961803B1 (fr) | 2010-06-29 | 2013-02-22 | Arkema France | Compositions acides pour l'elimination des oxalates |
-
2013
- 2013-10-09 PL PL13776762T patent/PL2917179T3/pl unknown
- 2013-10-09 KR KR1020157011702A patent/KR102158059B1/ko active IP Right Grant
- 2013-10-09 BR BR112015007192A patent/BR112015007192B1/pt not_active IP Right Cessation
- 2013-10-09 PT PT13776762T patent/PT2917179T/pt unknown
- 2013-10-09 MA MA38074A patent/MA20150407A1/fr unknown
- 2013-10-09 US US14/440,182 patent/US9573893B2/en active Active
- 2013-10-09 AU AU2013343772A patent/AU2013343772B2/en not_active Ceased
- 2013-10-09 ES ES13776762.0T patent/ES2684224T3/es active Active
- 2013-10-09 CA CA2890831A patent/CA2890831C/en not_active Expired - Fee Related
- 2013-10-09 CN CN201380050566.9A patent/CN104684892B/zh not_active Expired - Fee Related
- 2013-10-09 WO PCT/EP2013/071013 patent/WO2014072143A1/de active Application Filing
- 2013-10-09 SI SI201331132T patent/SI2917179T1/sl unknown
- 2013-10-09 EP EP13776762.0A patent/EP2917179B1/de active Active
- 2013-10-09 JP JP2015541060A patent/JP6104397B2/ja not_active Expired - Fee Related
- 2013-11-05 TW TW102140094A patent/TWI603952B/zh not_active IP Right Cessation
- 2013-11-06 UY UY0001035124A patent/UY35124A/es not_active Application Discontinuation
- 2013-11-08 AR ARP130104100A patent/AR093406A1/es active IP Right Grant
-
2015
- 2015-05-07 ZA ZA2015/03136A patent/ZA201503136B/en unknown
- 2015-11-10 HK HK15111061.4A patent/HK1210138A1/xx unknown
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
US9573893B2 (en) | 2017-02-21 |
UY35124A (es) | 2014-06-30 |
KR20150081280A (ko) | 2015-07-13 |
EP2917179A1 (de) | 2015-09-16 |
CA2890831A1 (en) | 2014-05-15 |
JP2015535297A (ja) | 2015-12-10 |
TWI603952B (zh) | 2017-11-01 |
MA20150407A1 (fr) | 2015-11-30 |
ES2684224T3 (es) | 2018-10-01 |
SI2917179T1 (sl) | 2018-09-28 |
AR093406A1 (es) | 2015-06-03 |
CN104684892B (zh) | 2017-08-29 |
TW201431835A (zh) | 2014-08-16 |
CN104684892A (zh) | 2015-06-03 |
BR112015007192A2 (pt) | 2017-07-04 |
PL2917179T3 (pl) | 2018-11-30 |
HK1210138A1 (en) | 2016-04-15 |
AU2013343772A1 (en) | 2015-03-19 |
JP6104397B2 (ja) | 2017-03-29 |
WO2014072143A1 (de) | 2014-05-15 |
PT2917179T (pt) | 2018-10-11 |
US20150291520A1 (en) | 2015-10-15 |
AU2013343772B2 (en) | 2017-06-15 |
KR102158059B1 (ko) | 2020-09-21 |
ZA201503136B (en) | 2016-01-27 |
CA2890831C (en) | 2020-04-21 |
BR112015007192B1 (pt) | 2019-09-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69508939T2 (de) | Persauerstoffverbindung enthaltende zusammensetzung | |
EP2917179B1 (de) | Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure | |
DE19812588C1 (de) | Härtestabilisierende Percarbonsäurelösungen, Verfahren zu deren Herstellung und deren Verwendung | |
DE69724645T2 (de) | Verfahren zur Herstellung von Percarbonsäurelösungen | |
DE19630615B4 (de) | Verfahren zum Reinigen und Desinfizieren von Oberflächen und Produktionsanlagen | |
EP0945404B1 (de) | Perameisensäure und Peressigsäure enthaltendes wässriges Desinfektionsmittel, Verfahren zu dessen Herstellung und dessen Verwendung | |
DE3543500C2 (ja) | ||
DE69911016T2 (de) | Verfahren zur herstellung einer wässrigen monoester percarbonsäurelösung | |
WO1996033947A1 (de) | Verfahren zur herstellung einer chlordioxid enthaltenden desinfektionslösung zur wasseraufbereitung | |
DE69005416T2 (de) | Stabilisierung von konzentrierten Wasserstoffperoxydlösungen. | |
DE3928747A1 (de) | Verfahren zur desinfektion von harten oberflaechen mit chlordioxid | |
DE19517465C1 (de) | Percarbonsäurelösungen mit verbesserter Stabilität im Kontakt mit Edelstahl | |
EP0136309A1 (de) | Verfahren zur herstellung einer modifizierten wässrigen chloritlösung, die danach hergestellte lösung sowie deren verwendung. | |
DE3403631C2 (ja) | ||
EP1730258B1 (de) | Reinigungs-, desinfektions- und indikatormittel | |
EP1916226B1 (de) | Verwendung eines organischen Reduktionsmittels zur Wasseraufbereitung durch Entfernung von Chloramin, Chlor und anderen Aktivchlorverbindungen aus Hälterungswasser für Wasserorganismen. | |
DE3843992C2 (ja) | ||
DE1804504A1 (de) | Verfahren zur Stabilisierung von Wasserstoffperoxyd enthaltenden alkalischen Bleichloesungen | |
DE1617236C3 (de) | Germicide Detergentien | |
WO2018195577A1 (de) | Zusammensetzung zur reinigung von oberflächen | |
DE3138245A1 (de) | "verfahren zur desinfektion eines bakterien enthaltenden waessrigen mediums" | |
DE1046003B (de) | Verfahren zur Stabilisierung von technischem AEthylendichlorid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20150429 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20180119 |
|
INTG | Intention to grant announced |
Effective date: 20180119 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502013010435 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1010500 Country of ref document: AT Kind code of ref document: T Effective date: 20180715 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2684224 Country of ref document: ES Kind code of ref document: T3 Effective date: 20181001 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Ref document number: 2917179 Country of ref document: PT Date of ref document: 20181011 Kind code of ref document: T Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20180829 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180920 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: NO Ref legal event code: T2 Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180921 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181020 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502013010435 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20190321 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181009 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181031 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181009 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 502013010435 Country of ref document: DE Owner name: EVONIK OPERATIONS GMBH, DE Free format text: FORMER OWNER: EVONIK DEGUSSA GMBH, 45128 ESSEN, DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: NO Ref legal event code: CHAD Owner name: EVONIK OPERATIONS GMBH, DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A Owner name: EVONIK OPERATIONS GMBH Effective date: 20200623 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180620 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20131009 Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180620 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: HC Owner name: EVONIK OPERATIONS GMBH; DE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGEMENT DE NOM DU PROPRIETAIRE; FORMER OWNER NAME: EVONIK DEGUSSA GMBH Effective date: 20200403 |
|
REG | Reference to a national code |
Ref country code: FI Ref legal event code: PCE Owner name: EVONIK OPERATIONS GMBH |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: HC Owner name: EVONIK OPERATIONS GMBH; DE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME Effective date: 20200928 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NO Payment date: 20201026 Year of fee payment: 8 Ref country code: AT Payment date: 20201022 Year of fee payment: 8 Ref country code: PT Payment date: 20201002 Year of fee payment: 8 Ref country code: FI Payment date: 20201022 Year of fee payment: 8 Ref country code: SE Payment date: 20201028 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SI Payment date: 20201006 Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: HC Ref document number: 1010500 Country of ref document: AT Kind code of ref document: T Owner name: EVONIK OPERATIONS GMBH, DE Effective date: 20210315 |
|
REG | Reference to a national code |
Ref country code: SI Ref legal event code: SP73 Owner name: EVONIK OPERATIONS GMBH; DE Effective date: 20210714 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20210930 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20211020 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20211020 Year of fee payment: 9 Ref country code: ES Payment date: 20211224 Year of fee payment: 9 Ref country code: TR Payment date: 20211007 Year of fee payment: 9 Ref country code: GB Payment date: 20211022 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20211028 Year of fee payment: 9 Ref country code: FR Payment date: 20211022 Year of fee payment: 9 Ref country code: BE Payment date: 20211020 Year of fee payment: 9 |
|
REG | Reference to a national code |
Ref country code: NO Ref legal event code: MMEP |
|
REG | Reference to a national code |
Ref country code: FI Ref legal event code: MAE |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 1010500 Country of ref document: AT Kind code of ref document: T Effective date: 20211009 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211010 Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220411 Ref country code: NO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211010 Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211009 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211009 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502013010435 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20221101 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20221031 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20221009 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221101 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221031 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230503 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221009 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221009 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20231128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221009 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221010 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221010 |